This invention relates to the use of geraniol-containing compositions consisting essentially of (i) from 50-100% by weight of geraniol having the structure: ##STR1## and/or a geraniol precursor (e.g., geranyloxy-1,3,2-dioxaborinane having the structure: ##STR2## or beta-geraniol glucocide having the structure: ##STR3## with (in cases where substantially pure geraniol is not used) the remainder of the composition being (ii) a compound selected from the group consisting of citronellol having the structure: ##STR4## and nerol having the structure: ##STR5## as repellents against house flies (Musca domestica L.(Diptera:Muscidae)), Aedes aegypi, Culex nigripalpus, Aedes atlanticus, Culex salinarius, Aedes vexans, Culex spp., Simulium spp., Psoroferia ferox, Aedes infirmatus, Drosophila melanogaster, Coccinellidae, Anopheles crucians, Psoroferia columbiae, Culicoides spp., and Aedes spp.
This invention also relates to the use of such compounds and compositions of matter in insect repellent soaps and the like wherein, the compositions of matter are used as such or in combination in control release systems with polymers such as biodegradable polymers.
Unsaturated alcohols including 1-octen-4-ol and 1-nonen-3-ol are known with respect to controlling insects and 1-octen-4-ol and 1-nonen-3-ol are disclosed to be so useful in repelling Musca domestica L.(Diptera:Muscidae) and Aedes aegypti in U.S. Pat. No. 4,764,367 issued on Aug. 16, 1988 and U.S. Pat. No. 5,118,711 issued on Jun. 2, 1992. Several unsaturated alcohols have been found to attract insects and others have been found to repel such insects. Thus, U.S. Pat. No. 4,152,442 issued on May 1, 1979 sets forth 6-none-1-ol in a composition of matter used as an attractant for the male Mediterranean fruit fly. Chem.Abstracts, Volume 103, No. 71086p concerns the synthesis of (Z)-8-dodecen-1-ol and its acetate as pheromone components of the Oriental Fruit Moth (Grapholita molesta). This is an abstract of the article in Acta Chem. Scan. Ser. B, 1985, B39(4), pages 267-72. U.S. Pat. No. 4,364,931 issued on Dec. 21, 1982 discloses the use of 9(Z)-tetradecen-1-ol acetate in attracting male white-line dart moths.
Chem.Abstracts, Volume 80, 1974, at No. 117098f discloses the use of trans-6-none-1-ol acetate as an ovipositional attractant and stimulant of the melon fly. U.S. Pat. No. 2,254,665 issued on Sep. 1, 1941, on the other hand, discloses the use of aliphatic alcohols having from 10 to 14 carbon atoms to repel insects. Examples of the aliphatic alcohols of U.S. Pat. No. 2,254,665 are all saturated alcohols, to wit:
dodecyl alcohol; PA1 octyl alcohol; PA1 hexadecyl alcohol; PA1 tetradecyl alcohol; and PA1 undecyl alcohol. PA1 Item 5443-3-phenyl-2-octen-1-ol repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA1 Item 5444-2,6-dimethyl-4-octen-3-ol repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA1 Item 5445-3,6-dimethyl-5-octen-3-ol repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA1 Item 5446-3-6-dimethyl-5-octen-3-ol acetate repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA1 Item 5448-3,7-dimethyl-6-octen-1-ol repels the yellow fever mosquito from cloth at a level of "2" on a scale of 1-10. PA1 Item 5450-3,7-dimethyl-6-octen-2-ol repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA1 Item 5451-3,6-dimethyl-6-octen-3-ol repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA1 Item 5452-3,7-dimethyl-6-octen-3-ol repels the yellow fever mosquito from cloth at a level of "2" on a scale of 1-10. PA1 Yellow fever mosquito: "1" on a scale of 1-10 PA1 Tick at a level of "2" on a scale of 1-10. PA1 0.06% terpineol; PA1 0.05% citronella; PA1 0.08% rhodenol extract; and PA1 0.06% geraniol
U.S. Pat. No. 2,254,665 fails to disclose the use of unsaturated alcohols in insect repellent compositions.
Chem.Abstracts, Volume 74, 1974, at No. 99419f discloses various nonenyl acetates as attractants for female melon flies (abstract of J.Med.Chem. 1971, 14(3), pages 236-9) including trans-2-nonen-1-yl acetate.
On the other hand, Beroza, Materials Evaluated As Insecticides, Repellents and Chemosterilants at Orlando and Gainesville, Fla., 1952-1964. Agriculture Handbook No. 340, published by The Agricultural Research Service, U.S. Department of Agriculture, August, 1967 discloses the following items 5443-5452 as insect repellents (on a scale of 1-10) as follows:
Item 5447-2,7-dimethyl-5-octen-4-ol acetate repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10.
Item 5449-3,7-dimethyl-6-octen-1-ol carbanilate repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10.
Beroza, Agriculture Handbook No. 340 at Item 7977 indicates that undecyl alcohol acetate has insect repelling properties as follows:
European Published Patent Application 478,846 (abstracted at Chem.Abstracts, Volume 116:250531v discloses the use of borneol as an "environmentally friendly" ant repellent. U.S. Pat. No. 4,774,081 issued Sep. 27, 1988 and corresponding European Application 275,085 discloses as an example of a contact insect repellent against cockroaches and other crawling insects, citronellol, geraniol, nerol and butyl hydroxy anisole and mixtures thereof (column 2, lines 31-39). Chem.Abstracts, Volume 105:204742q discloses that compounds from the leaves of bay (Laurus nobilis L.) are useful repellents for Tribolium castaneum (Herbs) and these compounds include, inter alia, geraniol when present at 50 ppm. Chem.Abstracts, Volume 113:110945w (abstract of Japan Kokai Tokkyo Koho 02/67202) discloses that, inter alia, linaloolo. geraniol, citronellol and nerol are repellents when incorporated into porous inorganic microcapsules against cockroaches, slugs, ants, etc.. Chem.Abstracts, Volume 104:30390k discloses the repellency against house flies of citronellol.
However, attractancy of geraniol towards certain insect genuses is disclosed in "Handbook of Insect Pheromones and Sex Attractants", Mayer, et al, CRC Press, 1991 at pages 708,709, 866 and 867.
Biodegradable polymers containing insect repellents including polymers containing at least a major proportion of poly(epsilon caprolactone) homopolymers are disclosed by Munteanu, et al, in U.S. Pat. No. 4,496,467 issued on Jan. 29, 1985, U.S. Pat. No. 4,469,613 issued on Sep. 4, 1984 and U.S. Pat. No. 4,548,764 issued on Oct. 22, 1985.
Referring back to Beroza, Materials Evaluated As Insecticides, Repellents And Chemosterilants at Orlando and Gainesville, Fla., 1952-1964 (cited, supra) Beroza discloses that the compound having the structure: ##STR6## taken in admixture with the compound having the structure: ##STR7## have repellency against the yellow fever mosquito on cloth at a level of "2" on a scale of 1-10.
PCT Application 91/15118 published on Oct. 17, 1991 (Beldock, et al) alleges the use of a mixture of geraniol in combination with terpineol, citronella and rhodenol extract as repellents against ticks and biting flies including mosquitoes and black flies. It is alleged in PCT Application 91/15118 that the composition of matter TREO.RTM. containing:
is such a useful insect repellent composition.
Brattsten, "Cytochrome P-450 involvement in the Interactions between plant terpenes and insect herbivores", Chapter 10 of "Plant Resistance to Herbivores", ed. P. A. Hedin, pages 173-195, ACS Symposium Series 208, Washington, D.C., 1983 discloses the repellency of geraniol per se against house flies in Table II on page 179.
Prior art published prior to the instant invention followed by reduction to practice of the instant invention of the instant patent application does not teach applicants' invention.